Anthraquinone dyes

ABSTRACT

Dyes of the formula   &lt;IMAGE&gt;   where Hal is chlorine or bromine, X is hydrogen, hydroxyphenyl or alkoxyphenyl, n is 1 or 2, or, when X is hydroxyphenyl or alkoxyphenyl, may furthermore be O, R1, R2, R3 and R4 independently of one another are each unsubstituted or alkoxy-substituted alkyl, and R1 and R3 may furthermore be hydrogen, are of high color strength, and very useful for dyeing and printing cellulose-containing fiber material or cellulose swollen by means of water-miscible swelling agents.

The present invention relates to dyes of the general formula I ##STR2## where Hal is chlorine or bromine, X is hydrogen and n is 1 or 2, or X is hydroxyphenyl or C₁ -C₃ -alkoxyphenyl and n is 0, 1 or 2, and R² and R⁴ independently of one another are each unsubstituted or C₁ -C₈ -alkoxy-substituted C₁ -C₁₈ -alkyl, and R¹ and R³ independently of one another are each hydrogen or unsubstituted or C₁ -C₈ -alkoxy-substituted C₁ -C₁₈ -alkyl.

R¹, R², R³ and R⁴ are, for example, C₁ -C₁₈ -alkyl, C₁ -C₈ -alkoxy-C₂ -alkyl or C₁ -C₈ -alkoxy-C₃ -alkyl.

Specific examples of radicals R¹, R², R³ and R⁴ are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₂, C₈ H₁₇, C₁₀ H₂₁, C₁₂ H₂₅, C₁₈ H₃₇, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₉ and C₃ H₆ -O-C₈ H₁₇.

R² and R⁴ are each preferably C₁ -C₁₀ -alkyl, C₁ -C₄ -alkoxy-C₂ -alkyl or C₁ -C₄ -alkoxy-C₃ -alkyl, in particular C₁ -C₈ -alkyl, methoxyethyl or methoxypropyl. R¹ and R³ are each preferably hydrogen or C₁ -C₁₀ -alkyl, in particular hydrogen, methyl or ethyl.

Very particularly preferred dyes of the formula I are those where ##STR3## are each --N(CH₃)₂ or --NHCH₃, Hal is bromine, and n is 1. Among these dyes, those described in Examples 1 and 2 may be particularly singled out.

The compounds of the formula I can be prepared by reacting, for example, a halogenated diaminoanthrarufin of the formula ##STR4## where Hal, X and n have the above meanings, with a compound of the formula ##STR5## in a conventional manner.

The compounds I may also be prepared by first reacting (II) with an equimolar amount of cyanuric chloride, and then reacting the dichlorotriazinylaminoanthraquinone compound, in a conventional manner, with the appropriate amine or amine mixture ##STR6## give (I).

The reaction with the amines may be carried out either using a molar ratio of 1:2 or in two stages using equimolar amounts in each stage.

The dyes I can be obtained in the pure form corresponding to formula I, or as mixtures.

The Examples which follow illustrate the reaction; parts and percentages are by weight, unless stated otherwise.

The novel dyes are of high color strength, and are preferably used for dyeing and printing, by the process described in German Patent No. 1,811,796, cellulose-containing fiber material, in particular a cellulose polyester, or cellulose which has been swollen by means of a water-miscible swelling agent.

Fast dyeings are obtained, the lightfastness and wetfastness of which may be singled out.

EXAMPLE 1

52.5 parts of 1,5-dihydroxy-4,8-diamino-x-bromoanthraquinone and 33.5 parts of 2-chloro-4,6-bis-dimethylamino-s-triazine are stirred with 234 parts of o-dichlorobenzene. A gentle stream of nitrogen is passed over the mixture, which is refluxed, while stirring, until all the starting material has been consumed; this takes about 2-3 hours. Thereafter, the mixture is cooled to room temperature, while stirring slowly, and the resulting well-crystallized dye is filtered off rapidly, using a suction filter. The o-dichlorobenzene-moist filter cake is freed of solvent by steam distillation, a small amount of ammonia water being added until a clearly alkaline reaction is obtained. The product is filtered off under suction while still warm, washed neutral with warm water and dried, and 64.6 parts of a dark blue crystalline powder having a melting point of about 250° C. are obtained; analysis of this product gives the following formula: ##STR7##

On polyester/cotton, the dye gives very fast clear blue hues in very closely matching shades.

Instead of o-dichlorobenzene, other inert hydrocarbons, eg. toluene, xylene, chlorobenzene, trichlorobenzene, nitrobenzene, p-cymene, or alkylbenzene mixtures, may also be used successfully. Xylene, and alkylbenzene mixtures which are obtainable commercially under the name SOLVESSO, are particularly suitable.

EXAMPLE 2

78 parts of o-dichlorobenzene are taken, and a mixture of 7.5 parts of 1,5-dihydroxy-4,8-diamino-7-p-hydroxyphenylanthraquinone and 7.5 parts of 1,5-dihydroxy-4,8-diamino-7-p-methoxyphenylanthraquinone (100% strength, moist press cake) is stirred in 10.6 parts of 2-chloro-4,6-bis-diethylamino-s-triazine are added at room temperature.

The mixture is heated slowly to 100°-105° C. under a gentle stream of nitrogen, while stirring rapidly, and is kept at this temperature until a water/o-dichlorobenzene mixture no longer passes over. Thereafter, the mixture is refluxed and stirred until all the starting material has been consumed; this takes about 1/4-1/2 hour. It is then cooled to about 100° C., and the o-dichlorobenzene is stripped off by steam distillation, the suspension being rendered alkaline with a small amount of ammonia water. The dye is then filtered off under suction while still warm, and washed neutral with warm water. 22 parts of a dye mixture are obtained, which has a melting point of about 198° C. and differs from the starting material in that a hydrogen atom of an amino group has been replaced by a 4,6-bis-diethylamino-s-triazinyl radical. The dye gives very fast beautiful blue hues on polyester/cotton.

EXAMPLE 3

(a) Reaction of 1,5-dihydroxy-4,8-diamino-x-bromoanthraquinone with cyanuric chloride

73 parts of 1,5-dihydroxy-4,8-diamino-x-bromoanthraquinone in 400 parts of nitrobenzene are heated at about 200° C. under a gentle stream of nitrogen, while stirring, the distillate being collected in the descending condenser as long as drops of water pass over. Thereafter, the mixture is cooled to 100° C., 45 parts of cyanuric chloride are added a little at a time in the course of 20 minutes, and a gentle stream of nitrogen is again passed over the mixture, which is heated to 120° C. and stirred at this temperature until hydrogen chloride is no longer evolved; this is the case after from 3 to 4 hours. The mixture is cooled, and the product is then filtered off rapidly under suction; if the mixture has become too thick, it may be diluted with a small amount of toluene. The residue is washed with toluene until nitrobenzene can no longer be detected in the filtrate, and is then dried under reduced pressure. 84 parts of a dye intermediate of the formula: ##STR8## are obtained. (b) Reaction to give the dye

20 parts of the product obtained as described in Example 3(a) are introduced into 100 parts of dimethylformamide, and the mixture is heated, at 120° C., with 21 parts of 2-ethylhexylamine until all the starting material has reacted; this takes from 3 to 4 hours. The mixture is cooled to room temperature, and the resulting solution is added dropwise to a mixture of 1,000 parts of water, 1,000 parts of ice, 120 parts of methanol and 150 parts of glacial acetic acid, while stirring vigorously. The dye is precipitated in finely divided form, and the precipitate is washed with a large amount of water and dried under reduced pressure. 25.6 parts of a dye of the formula ##STR9## are obtained in the form of a dark blue crystalline powder having a melting point of about 180° C.

EXAMPLE 4

A mixture of 200 parts of water and 200 parts of 50% strength aqueous ethylamine is introduced into an autoclave. 20 parts of the product obtained as described in Example 3(a) are introduced, while stirring, and the mixture is stirred for 8 hours at about 100° C., in the closed autoclave. The content of the autoclave is cooled, let down, and diluted with water, the product is filtered off under suction, washed neutral with warm water and dried, and 16.6 parts of a dark blue crystalline dye of the formula ##STR10## are obtained. The dye has a melting point of 232° C., and dyes polyester/cotton in very fast beautiful blue hues.

EXAMPLES 5 TO 116

The following dyes of the formulae Ia, Ib and Ic are prepared by a procedure similar to that described in Examples 1, 2 or 3, and 4.

    __________________________________________________________________________     Ex-                                                                            ample                                                                              n  Hal                                                                               R.sup.1                                                                            R.sup.2  R.sup.3                                                                            R.sup.4  Hue                                        __________________________________________________________________________      ##STR11##                          (Ia)                                       5   1  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       6   1  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       7   1  Br H   CH.sub.3 H   CH.sub.3 blue                                       8   1  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       9   1  Br H   CH.sub.3 H   C.sub.2 H.sub. 5                                                                        blue                                       10  1  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       11  1  Br H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       12  1  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       13  2  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       14  2  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       15  2  Br H   CH.sub.3 H   CH.sub.3 blue                                       16  2  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       17  2  Br H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       18  2  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       19  2  Br H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       20  2  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       21  1  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       22  1  Cl CH.sub.3                                                                           CH.sub. 3                                                                               C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       23  1  Cl H   CH.sub.3 H   CH.sub.3 blue                                       24  1  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       25  1  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       26  1  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       27  1  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       28  1  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       29  2  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       30  2  Cl CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       31  2  Cl H   CH.sub.3 H   CH.sub.3 blue                                       32  2  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       33  2  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       34  2  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       35  2  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       36  2  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                        ##STR12##                          (Ib)                                       37  0  -- C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       38  0  -- CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       39  0  -- H   CH.sub.3 H   CH.sub.3 blue                                       40  0  -- H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       41  0  -- H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       42  0  -- H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       43  0  -- H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       44  0  -- H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       45  1  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sup.5                                                                         blue                                       46  1  Cl CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       47  1  Cl H   CH.sub.3 H   CH.sub.3 blue                                       48  1  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       49  1  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       50  1  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       51  1  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       52  1  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       53  2  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       54  2  Cl CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       55  2  Cl H   CH.sub.3 H   CH.sub.3 blue                                       56  2  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       57  2  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       58  2  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       59  2  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       60  2  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       61  1  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       62  1  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       63  1  Br H   CH.sub.3 H   CH.sub.3 blue                                       64  1  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       65  1  Br H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       66  1  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       67  1  Br H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       68  1  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       69  2  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       70  2  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       71  2  Br H   CH.sub.3 H   CH.sub.3 blue                                       72  2  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       73  2  Br H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       74  2  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       75  2  Br H   (CH.sub.2 CH(CH.sub.3).sub.2                                                            H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       76  2  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                        ##STR13##                          (Ic)                                       77  0  -- C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       78  0  -- CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       79  0  -- H   CH.sub.3 H   CH.sub.3 blue                                       80  0  -- H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       81  0  -- H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       82  0  -- H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       83  0  -- H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       84  0  -- H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       85  1  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub. 5                                                                        C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       86  1  Cl CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       87  1  Cl H   CH.sub.3 H   CH.sub.3 blue                                       88  1  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       89  1  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       90  1  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       91  1  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       92  1  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       93  2  Cl C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       94  2  Cl CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       95  2  Cl H   CH.sub.3 H   CH.sub.3 blue                                       96  2  Cl H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       97  2  Cl H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       98  2  Cl H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       99  2  Cl H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       100 2  Cl H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       101 1  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       102 1  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       103 1  Br H   CH.sub.3 H   CH.sub.3 blue                                       104 1  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       105 1  Br H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       106 1  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       107 1  Br H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       108 1  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       109 2  Br C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       110 2  Br CH.sub.3                                                                           CH.sub.3 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         blue                                       111 2  Br H   CH.sub.3 H   CH.sub.3 blue                                       112 2  Br H   C.sub.2 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                         blue                                       113 2  Br H   CH.sub.3 H   C.sub.2 H.sub.5                                                                         blue                                       114 2  Br H   CH(CH.sub.3).sub.2                                                                      H   CH(CH.sub.3).sub.2                                                                      blue                                       115 2  Br H   CH.sub.2 CH(CH.sub.3).sub.2                                                             H   CH.sub.2 CH(CH.sub.3).sub.2                                                             blue                                       116 2  Br H   (CH.sub.2).sub.2 OCH.sub.3                                                              H   (CH.sub.2).sub.2 OCH.sub.3                                                              blue                                       __________________________________________________________________________ 

We claim:
 1. A dye of the formula ##STR14## where X is hydrogen, 4-hydroxyphenyl or 4-methoxyphenyl, and ##STR15## are each independently --N(CH₃)₂ or --NHCH₃.
 2. The dye as claimed in claim 1, wherein X is hydrogen and ##STR16## are each --N(CH₃)₂. 